Toughened epoxy adhesive composition
View Patent ↗The invention is an epoxy resin based adhesive composition comprising an epoxy resin and a compound comprising an elastomeric prepolymer residue selected from the group of a polyurethane, a polyurea and a polyurea polyurethane having isocyanate end groups, the isocyanate end groups of said prepolymer residue being capped by a capping compound selected from the group consisting of a primary aliphatic, cycloaliphatic, heteroaromatic and araliphatic amine, a secondary aliphatic, cycloaliphatic, aromatic, heteroaromatic and araliphatic amine, a thiol and an alkyl amide, said capping compound being bound to the end of the polymer chain of the elastomeric prepolymer in a manner such that the end to which it is bonded no longer has a reactive group. In addition to the capping compound defined above above, a capping compound selected from the group consisting of a phenol and a polyphenol can be used for capping the isocyanate end groups of the prepolymer residue.
1. A curable epoxy composition comprising:
a) 30 to 80 percent by weight of an epoxy resin;
b) 5 to 40 percent by weight of a compound comprising an elastomeric prepolymer residue selected from the group of a polyurethane, a polyurea and a polyurea polyurethane having isocyanate end groups, the isocyanate end groups of said prepolymer residue being capped by a monofunctional capping compound selected from the group consisting of secondary aliphatic amines, secondary cycloaliphatic amines, secondary aromatic amines, secondary heteroaromatic amines, secondary araliphatic amines, thiols, alkyl amides, and mixtures thereof, wherein the capping compound is bound to the end of the polymer chain of the elastomeric prepolymer in a manner such that the end to which it is bonded no longer has a reactive group;
c) 5 to 30 percent by weight of a core shell rubber, a second epoxy resin modified with a copolymer based on a 1,3-diene and a polar, ethylenically unsaturated comonomer or a mixture thereof; and
d) 1 to 10 percent by weight of a hardener.
2. A curable epoxy composition according to claim 1 wherein the capped elastomeric prepolymer corresponds to the structure of the formula
wherein R 1 is the elastomeric prepolymer residue, said residue having a valence of 2 to 6 with p=2 to 6,
Y is the residue of the secondary aliphatic, secondary cycloaliphatic amine, secondary aromatic amine, secondary heteroaromatic amine, secondary araliphatic amine, thiol and/or alkyl amide;
said compound being soluble or dispersible in an epoxy resin.
3. A curable epoxy resin composition according to claim 1 wherein the capped elastomeric prepolymer is obtainable by reacting a polyether polyol and/or a polyether polyamine with an excess of a polyisocyanate.
4. A curable epoxy resin composition according to claim 3 wherein during the reaction to obtain the capped elastomeric prepolymer additionally a polyester diol, a polybutadiene diol and/or a short-chain polyol is co-reacted.
5. A curable epoxy composition according to claim 1 wherein the secondary amine is dicyclohexylamine and/or diisopropylamine.
6. A curable epoxy composition according to claim 1 wherein the thiol is 1-dodecanethiol.
7. A curable epoxy composition according to claim 1 comprising
a) 40 to 70 weight percent of epoxy resin;
b) about 8 weight percent to about 30 weight percent of the capped elastomeric prepolymer;
c) about 10 weight percent to about 20 weight percent of the core shell rubber, a second epoxy resin modified with a copolymer based on a 1,3-diene and polar, ethylenically unsaturated comonomer or mixture thereof; and
d) about 2 to about 7 weight percent of hardener.
8. A curable epoxy composition according to claim 1 further comprising one or more additives selected from the group of hardeners, accelerators, adhesion promoters, epoxy silane, fumed silica, wetting agents and inorganic fillers.
9. A curable epoxy composition according to claim 1 further comprising a thermoplastic polymer comprising a polyester segment, said polymer being at least partially crystalline at room temperature and having a softening temperature in the range of 40° to 125°C.
10. A curable epoxy composition according to claim 1 further comprising as an accelerator 2,4,6-tris(dimethylaminomethyl)phenol integrated into a poly(p-vinylphenol) matrix.
11. A process of bonding together separate surfaces wherein the curable epoxy composition according to claim 1 is applied to at least one surface, the surfaces are brought together and the epoxy composition is cured at a temperature of 120° C. to 210°C.
12. A curable epoxy composition according to claim 1 wherein the epoxy resin has the residue of bisphenol moieties in the backbone.
13. A curable epoxy composition according to claim 12 wherein the epoxy resin comprises a mixture of liquid and solid resins wherein the solid epoxy resin comprises about 40 percent by weight or less of the epoxy resin mixture.
14. A curable epoxy composition according to claim 12 wherein the isocyanate used to prepare the elastomeric prepolymer is an aliphatic polyisocyanate.
15. A curable epoxy composition according to claim 1 wherein the elastomeric prepolymer residue is derived from the reaction of a polyether polyol and a polyisocyanate wherein the polyether polyol comprises a polytetrahydrofuran or a polypropylene oxide and the isocyanate is an aliphatic polyisocyanate.
16. A curable epoxy compound according to claim 15 wherein the capping compound is dicyclohexylamine and/or diisopropylamine.
17. A curable epoxy composition comprising:
a) an epoxy resin;
b) a compound comprising an elastomeric prepolymer residue selected from the group of a polyurethane, a polyurea and a polyurea polyurethane having isocyanate end groups, the isocyanate end groups of said prepolymer residue being capped by a mixture of monofunctional capping compounds the first selected from the group consisting of secondary aliphatic amines, secondary cycloaliphatic amines, secondary aromatic amines, secondary heteroaromatic amines, secondary araliphatic amines, thiols, alkyl amides, and mixtures thereof, and the second selected from monofunctional phenols wherein the capping compound is bound to the end of the polymer chain of the elastomeric prepolymer in a manner such that the end to which it is bonded no longer has a reactive group;
c) a core shell rubber, a second epoxy resin modified with a copolymer based on a 1,3-diene and a polar, ethylenically unsaturated comonomer or a mixture thereof; and
d) a hardener.
18. A curable epoxy composition according to claim 17 wherein capped elastomeric prepolymer corresponds to the structure of Formula I
wherein R1 is the elastomeric prepolymer residue, said residue having a valence of p+q=2 to 6 with p=1 to 6 and q is greater than 0 to 5,
X is the residue of the secondary aliphatic amine, secondary cycloaliphatic amine, secondary aromatic amine, secondary heteroaromatic amine, secondary araliphatic amine the thiol and/or the alkyl amide and
Y is the residue of the phenol;
said compound being soluble or dispersible in an epoxy resin.